Long term ageing of polyamide 6 and polyamide 6 reinforced with 30% of glass fibers: temperature effect

Because the prediction of the durability of polyamide materials is a very important issue for designers and users, the effect of environment conditions on their mechanical properties is an active field of research. For this reason this experimental investigation was conducted in order to study the effect of temperature on long term ageing of polyamide 6 (PA6) and polyamide 6 reinforced with 30 wt% of glass fibers (PA6GF30). Ageing was realized in distilled water (pH?≈?6; 100% RH) at 30 °C, 50 °C, 70 °C and 90 °C for up to 80 days. Results highlighted the impact of ageing temperature on both conditioned materials. Thus, several surface damages such as crazing and yellowness were recorded especially at high temperatures indicating the materials degradation. These structure changes were induced by the combined effects of water and temperature. As the water diffuses within the polymer, the glass transition temperature T_g drops progressively with ageing temperature to reach the lowest value for samples aged at 90 °C for both tested materials. This tendency was also observed for Young’s modulus, tensile strength and the elongation at break. Thus, a significant loss in stiffness and strength of both materials was recorded as a function of conditioning temperature. This loss of mechanical properties is mainly caused by hydrolysis process and/or interfacial debonding. The appearance of this irreversible phenomenon rises with ageing temperature. Moreover, contrarily to PA6GF30, the temperature effect was also pointed out on SEM observations of PA6 samples. Thus, the hygrothermal ageing induces a change in the mode of fracture from ductile to moderate brittle one according to the ageing temperature. Accordingly, it seems that the ageing temperature has a great effect on the severity of damage of tested materials after long term immersion.     

Thermal and mechanical behavior of polyamide 6/polyamide 6I/6T blends

The thermal and mechanical properties of blends, obtained by mixing polyamide 6 (PA6) and an amorphous aromatic copolyamide G21 (ISO nomenclature PA 6I/6T), were investigated by differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. Quenched blends show a single glass transition temperature; the T_g-composition trend was interpreted by means of the Gordon–Taylor equation. The half-time of crystal-lization decreases by increasing the G21 content and this indicates a depression of the overall crystallization rate. A small decrease in the equilibrium melting temperature of PA6 in the blends was observed; this finding suggests that the interaction parameter in PA6/G21 blends is probably very small. The dynamic mechanical analysis of crystallized blends suggests the presence of a homogeneous amorphous phase even if the crystallization of PA6 occurred. The tensile mechanical properties reveal that G21 acts as stiffener of PA6. The collected experimental data suggest that PA6 and G21 are miscible in the composition range investigated. © 1996 John Wiley & Sons, Inc.     

Novel composite nanofibers based on polyamide 66/graphene oxide- grafted aliphatic- aromatic polyamide: preparation and characterization

New polyamide 66/graphene oxide (GO)-grafted aliphatic-aromatic polyamide (polyamide-imide) (PAI) (PA66/GOF) composites nanofibers were successfully prepared via electrospinning method for the first time. An polyamide imide (PAI) was synthesized using polycondensation reaction from a dicarboxylic acid and a diamine based on 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy) dianiline, and characterized by ¹HNMR and FTIR. Morphological, structural, thermal and mechanical characteristics of the nanocomposite fibers were investigated by means of SEM, TEM, WAXD, DMTA and TGA techniques. Composites nanofibers of PA66/GO, PA66/PAI and PA66/GOF with smooth surface, uniform structure as well as with diameter ranging from 195 to 784 nm were obtained. The GO incorporation caused a reduction in the nanofibers diameters. The TEM images showed that the GO was well dispersed in the PA66 nanofibers without significant aggregation. An approximately 10 °C temperature increase in the glass transition temperature of PA66 was achieved by addition of 0.5 wt% of PAI, resulting from aliphatic-aromatic structure of PAI. By the TGA results, an increase about 40 °C was observed in the thermal stability of PA66/PAI composite nanofibers in comparison with that of pure PA66 nanofibers.     

Blends of polyamide 6 and bisphenol-A polycarbonate. Effects of interchange reactions on morphology and mechanical properties

Blends of polyamide 6 (PA6) and polycarbonate (PC) were prepared in a Brabender mixer, at 240°C, applying long mixing time, for 45 min. It was observed that the morphology and the mechanical properties tend to resemble those of a homogeneous material as the mixing time and PA6 concentration increase. This is attributed to chemical reactions taking place between the two homopolymers. Acidolysis, amidolysis, and aminolysis, catalyzed by the terminals and the amide groups of the polyamide, should in principle be possible. Our results indicate that the aminolysis is the main process, inducing simultaneously scission of PC chains and formation of PC-PA6 copolymer chains. The latter act as interfacial agents between incompatible PA6 and PC, improving the mechanical properties of PA6-rich blends, in agreement with the predictions of some theoretical models assuming good phase interpenetration. © 1992 John Wiley & Sons, Inc.     

Effect of nanoparticle and glass fiber on the hydrothermal aging of polyamide 6

Hydrothermal aging behavior of polyamide 6 (PA6) and its composites (PA6/calcium carbonate [CaCO₃] and PA6/short glass fiber [SGF]) was systematically investigated using infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, and wide-angle X-ray diffraction as well as mechanical measurements. It was found that the water absorption mechanism is strongly affected by the presence of fillers. SGF-reinforced PA6 composites absorb less water than PA6 and PA6/CaCO₃ composites under the same hydrothermal condition. PA6 with 10 wt% SGF exhibits great resistance to hydrothermal aging, which is attributed to the higher crystallinity and larger α-form fraction.     

Study on the long‐term thermal‐oxidative aging behavior of polyamide 6

The long‐term thermal‐oxidative aging behavior of polyamide 6 (PA6) was studied by comparison with the stabilized sample in this work. The variation of mechanical properties of the pure and the stabilized samples of PA6 with aging time at 110°C, 130°C, and 150°C were investigated, respectively. The aging mechanism of PA6 under heat and oxygen was studied in terms of the reduced viscosity, crystallization behavior, dynamic mechanical behavior, and chemical composition through the methods of polarized light microscopy (PLM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X‐ray photoelectron energy spectrum (XPS), and so on. The results indicated that at the initial stage of aging, the molecular crosslinking reaction of PA6 dominated resulting in the increase of the mechanical strength, reduced viscosity, and the glass transition temperature of the sample. And the molecular degradation dominated in the subsequent aging process resulting in the decrease of the melting temperature, the increase of the crystallinity, and the formation of the oxides and peroxides products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Elevated temperature nanoindentation behaviour of polyamide 6

It has been found, in this study, that there is no close correlation between the tensile and nanoindentation moduli of polyamide 6 (PA6) at high temperatures. It is demonstrated that heat modifies the surface of PA6 specimens, but its effect on the nanomechanical properties is minor. The main spurious factor which affects the nanoindentation results is adhesion, especially at low indentation depths. The overestimation in the measured indentation moduli can be corrected by performing indentations with loads high enough so that the modulus is independent of the applied load. It is concluded that the lack of strict correlations between the tensile and indentation moduli (after corrections of adhesion) is caused by the shift in the glass transition temperature of PA6 owing to the hydrostatic stress imposed by the indenter. Further proof is given with two examples on hydrostatic pressure‐dependent polymers: polytetrafluoroethylene and polycarbonate. Copyright © 2011 Society of Chemical Industry     

Crystal structures and their effects on the properties of polyamide 12/clay and polyamide 6–polyamide 66/clay nanocomposites

Both polyamide 12 (PA 12)/clay and polyamide 6–polyamide 66 copolymer (PA 6/6,6)/clay nanocomposites were prepared by melt intercalation. The incorporation of 4–5 wt % modified clay largely increased the strength, modulus, heat distortion temperature (HDT), and permeation resistance to methanol of the polyamides but decreased the notched impact strength. Incorporation of the clay decreased the melt viscosities of both the PA 12 and PA 6/6,6 nanocomposites. Incorporation of the clay increased the crystallinity of PA 6/6,6 but had little effect on that of PA 12, which explained why the clay obviously increased the glass‐transition temperature of PA 6/6,6 but hardly had any effect on that of PA 12. The dispersion and orientation of both the clay and the polyamide crystals were studied with transmission electron microscopy, scanning electronic microscopy, and X‐ray diffraction. The clay was exfoliated into single layers in the nanocomposites, and the exfoliated clay layers had a preferred orientation parallel to the melt flow direction. Lamellar crystals but not spherulites were initiated on the exfoliated clay surfaces, which were much more compact and orderly than spherulites, and had the same orientation with that of the clay layers. The increase in the mechanical properties, HDT, and permeation resistance was attributed to the orientated exfoliated clay layers and the lamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4782–4794, 2006     

Flame retarding glass fibers reinforced polyamide 6 by melamine polyphosphate/polyurethane‐encapsulated solid acid

Melamine polyphosphate and thermal‐plastic polyurethane (TPU)‐encapsulated solid acid were applied for flame retardant glass fibers reinforced polyamide 6 (GFPA6). The introduction of TPU would change the interfacial property between glass fibers (GFs) and polyamide 6 (PA6), weakening the “candlewick effects” of GFs in PA6. Serving as a synergist, solid acid containing sulfur (CAS) played the role of a strong acid source, which could promote the system to form much more condensed and closed char layers. Macromolecular charring agent, TPU, was able to accelerate the charring process. In addition, TPU encapsulating on the unstable solid acid could isolate CAS from PA6 resin, preventing the chemical interaction between them, which would cause the degradation of material. This established technology provided an effective approach to prepare halogen‐free flame retardant GFPA6 with UL94‐1.6 mm V0 rating and good mechanical performance, showing a promise in the future commercial application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermal stabilization effect of biphenol monoacrylate on polyamide 6

Biphenol monoacrylate (AL) was combined with a traditional hindered phenolic‐based binary antioxidant system to form a ternary stabilization system for the purpose of further improving the thermal–oxidative stability of polyamide 6 (PA6). The thermal stabilization effect of the antioxidant AL on PA6 was studied in terms of the reduced viscosity, the chemical structure, the yellow index, and the mechanical properties. The results showed that the antioxidant AL, with the proper chemical structure, could improve the thermal stability of PA6 effectively through a unique bifunctional stabilizing mechanism. The interaction of the molecules of PA6 with the antioxidant AL was investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blends of polyamide 6 with bisphenol-A polycarbonate. I. Thermal properties and compatibility aspects

Blends of polyamide 6 (PA6) and polycarbonate (PC) have been investigated, over a full range of composition, to check interactions between them. SEM observations show that the mixtures are characterized by domains of clearly segregated homophases and voids between the two polymers. DSC and DMTA data indicate the presence of two T_g' s, corresponding to two separate phases, with the T_g of the PC phase decreasing on increasing the PA6 amount. Moreover, the crystallization kinetics of PA6 is slightly showed down by the PC. Chemical reactions between the two polymers are supposed to give rise to low molar mass compounds, as shown by GPC; these species plasticize the PC and partially dissolve into the molten polyamide, causing decrease of PC T_g and reduction of overall crystallization rate of PA6. Apparent influence of PC on melting temperature and enthalpy of PA6 is also discussed.     

Properties and morphology of supertoughened polyamide 6 hybrid composites

In this study, supertoughened polyamide (PA) nanocomposites were prepared by the incorporation of epoxidized polyhedral oligomeric silsesquioxane (POSS) into the polyamide 6 (PA6)/methyl methacrylate–butadiene–styrene copolymer (MBS) blend via a melt‐blending method. The effect of POSS on the rheological properties, mechanical properties, water uptake, and morphology of the hybrid PA6 nanocomposites was studied. The results show that under impact loading, the hybrid PA6 composites exhibited significant improvements in both the crack initiation energy and the crack propagation energy. This hybrid composite showed supertough behavior. Meanwhile, the tensile strength and the water absorption resistance was also improved with the addition of epoxidized POSS. The capillary and torque rheological results indicated that the epoxidized POSS, which acted as nanoscale ball bearings, significantly decreased the melt viscosity of the matrices and facilitated the melting process. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were performed to study the microstructure–property relationships of the hybrid PA6 composites. The TEM results showed that the MBS particles were dispersed homogeneously in the PA6 matrix. The mean diameter of the MBS particles decreased, and the size distribution of the MBS particles narrowed down with the introduction of the epoxidized POSS and compatiblizer. The SEM micrographs indicated that the impact fracture surfaces of the PA composites showed morphological characteristics of supertough polymers because of the synergistic effect of the functionalized POSS and compatibilized MBS particles. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of epoxy resin on the properties of maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer toughened polyamide 6 blends

Maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer (ABS‐g‐MA) was used as an impact modifier of polyamide 6 (PA6). Epoxy resin was introduced into PA6/ABS‐g‐MA blends to further improve their properties. Notched Izod impact tests showed that the impact strength of PA6/ABS‐g‐MA could be improved from 253 to 800 J/m with the addition of epoxy resin when the ABS‐g‐MA content was set at 25 wt %. Differential scanning calorimetry results showed that the addition of epoxy resin made the crystallization temperature and melting temperature shift to lower temperatures; this indicated the decrease in the PA6 crystallization ability. Dynamic mechanical analysis testing showed that the addition of epoxy resin induced the glass‐transition temperature of PA6 and the styrene‐co‐acrylonitrile copolymer phase to shift to higher temperatures due to the chemical reactions between PA6, ABS‐g‐MA, and epoxy resin. The scanning electron microscopy results indicated that the ABS‐g‐MA copolymer dispersed into the PA6 matrix uniformly and that the phase morphology of the PA6/ABS‐g‐MA blends did not change with the addition of the epoxy resin. Transmission electron microscopy showed that the epoxy resin did not change the deformation mechanisms of the PA6/ABS‐g‐MA blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Atmospheric-pressure plasma treatment of polyamide 6 composites for bonding with polyurethane

An atmospheric-pressure plasma jet (APPJ)-based surface treatment process was investigated for the structural (τ_B > 15 MPa) adhesive bonding of polyamide 6 (PA6) composites. The treated surfaces were examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM). Additionally, the shear strengths of single lap specimens were determined as a function of different plasma intensities and polyurethane adhesives. Our results show that APPJ leads to an increase of the surface free energy, oxygen concentration, and number of functional groups. Furthermore, the topography of the surface was significantly modified by exposure to APPJ. AFM measurements show that special attention has to be paid to the intensity of the plasma treatment to avoid melting and flattening of the PA6 surface on the nanometer scale. With optimized multiple APPJ treatments, lap shear strength of 20 MPa was achieved for the first time for this material system, allowing the material system to be employed in future automobile applications.     

Effects of polyamide 6 incorporation to the short glass fiber reinforced ABS composites: an interfacial approach

The properties of 30 wt% short glass fiber (SGF) reinforced acrylonitrile-butadiene-styrene (ABS) terpolymer and polyamide 6 (PA6) blends prepared with extrusion were studied using the interfacial adhesion approach. Work of adhesion and interlaminar shear strength values were calculated respectively from experimentally determined interfacial tensions and short beam flexural tests. The adhesion capacities of glass fibers with different surface treatments of organosilanes were evaluated. Among the different silanes tested, γ-aminopropyltrimethoxysilane (APS) was found to be the best coupling agent for the glass fibers, possibly, because of its chemical compatibility with PA6. Tensile test results indicated that increasing amount of PA6 in the polymer matrix improved the strength and stiffness of the composites due to a strong acid–base interaction at the interface. Incorporation of PA6 to the SGF reinforced ABS reduced the melt viscosity, broadened the fiber length distributions and increased the toughness of the composites. Fractographic analysis showed that the incorporation of PA6 enhanced the interactions between glass fibers and the polymeric matrix.     

Crystallization and dissolution behaviour of polyamide 6–water systems under pressure

The solubility of polyamide 6 (PA6) in water under pressure has been reported recently and is explored further here using a pressurized differential scanning calorimeter equipped with a pressure regulator, enabling operation at constant pressure. The optimum parameters for solubility (temperature, pressure, concentration) were determined. Crystallization and melting temperature depressions of a maximum of 60 °C were found. The minimum water concentration needed to reach the maximum temperature depression was found to be approximately 30 mass%. Because in such a case the end melting/dissolution temperature for PA6 in water is approximately 165 °C, the pressure level has to be high enough to prevent water from evaporating, i.e. above 8 bar (0.8 MPa). The expected industrial uses of the water solubility of polyamides under pressure are to ease the processing of polyamides by extrusion; to make polyamide composites; to disperse temperature‐sensitive fillers in polyamides; and, in general, to realize ‘green’ routes for the formation of polyamides. Copyright © 2010 Society of Chemical Industry     

Stress–thermooxidative aging behavior of polyamide 6

The long‐term stress–thermooxidative aging behavior of polyamide 6 (PA6) was studied in terms of the creep behavior, mechanical properties, chemical structure, crystallization, and orientation behavior. During aging, a thermooxidation reaction occurred, which included molecular chain degradation and crosslinking, in PA6. Meanwhile, when the samples were subjected to stress, crystallization, orientation, and chain scission were induced. In the initial stages of aging, the stress‐induced crystallization and orientation dominated; this resulted in an increase in the creep deformation, mechanical strength, crystallinity, and orientation factor. Molecular degradation and chain scission dominated in the subsequent aging process and resulted in a decrease of the mechanical strength, reduced viscosity, crystallinity, and orientation factor and an increase in the formation of oxide and peroxide products. The stress may have promoted the chain scission of PA6 during thermal aging and resulted in a decrease in the reduced viscosity and an increase in the carboxylic acid concentration. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of thermooxidative aging on the static and dynamic mechanical properties of long‐glass‐fiber‐reinforced polyamide 6 composites

The static and dynamic mechanical properties, thermal behaviors, and morphology of pure long‐glass‐fiber‐reinforced samples [polyamide 6 (PA6)/long glass fiber (LGF)] with different thermal exposure times at 160°C were studied by comparison with stabilized samples in this study. The aging mechanism of the PA6/LGF samples under heat and oxygen was studied with the methods of thermal Fourier transform infrared (FTIR), differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy (SEM), and so on. The results indicate that the static mechanical strength, melting temperature, and crystallization temperature decreased because of the decomposition of the macromolecular chain of PA6 resin and the debonding of the interface between the glass fibers and matrix. The glass‐transition temperature and crystallinity also increased and decreased, respectively, after aging. The macromolecular chain decomposition dominated in the subsequent aging process; this resulted in many sharp and brittle microcracks appearing on the surfaces of the aged samples, as shown by SEM and the FTIR spectra. The existence of stabilizers endowed the PA6/LGF composites with better retention of static and dynamic mechanical properties. The reason was that the metal ions of the copper salt antioxidant acted as an anti‐aging catalyst in the reinforced PA6 system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39594.     

Polydimethylsiloxane wrapped aluminum diethylphosphinate for enhancing the flame retardancy of polyamide 6

Aluminum diethylphosphinate (ADP) was wrapped with polydimethylsiloxane (PDMS) by a facile method to improve its hydrophobic properties. The morphology and properties of PDMS-modified ADP (PDMS-ADP) were investigated by thermogravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and water contact angle tests. The water contact angle of PDMS-ADP was increased from 126° to 151° as compared with that of ADP, which indicates that PDMS-ADP showed good hydrophobic properties. Then, ADP and PDMS-ADP were introduced into polyamide 6 (PA6) matrices to study the flame retardancy of the composites. The flammability of the PA6/ADP and PA6/PDMS-ADP composites was much lower than that of pure PA6. The composites PA6-1 (with the addition of 15 wt% ADP) and PA6-4 (with the addition of 12 wt% PDMS-ADP) could pass the UL-94 V-0 in the vertical burning test. Meanwhile, the peak heat release rates of PA6-1 and PA6-4 were 212 and 192 kW/m², with reductions of 67.3 and 70.4%, respectively, compared with pure PA6. These results indicated that the coating of PDMS could enhance the flame-retardant efficiency of ADP.     

Blends of polyamide 6, polycarbonate,and poly(propylene oxide). II. Reactive compatibilization–thermal degradation relationships

The thermal degradation of some blends of polyamide 6/polycarbonate (PA6/PC) and polyamide 6/polycarbonate/poly(propylene oxide) (PA6/PC/PPO) were investigated. The copolymer formed during the mixing of polyamide 6 and polycarbonate, at 240°C, for 30 min, increases the thermal stability of PA6/PC and of PA6/PC/PPO blends. This increase in the thermal stability occurs due to the plasticizing effect of PPO, which increases the mobility of the molecules of PA6 and PC, and consequently increases the probability of the reaction between the —NH₂ and —O—CO—O groups of polyamide 6 and polycarbonate, respectively. The ternary blends with PPO (5–10% w/w) have lower thermal stability than PA6/PC blends. This is due to the decrease of miscibility between these polymers and the rise of the diluting effect. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2556–2562, 2001